A method of producing a catalyst for stereospecific polymerization of propylene

 

(57) Abstract:

A method of producing a catalyst for stereospecific polymerization of propylene, based on titanium trichloride printed on porous media designed to produce active catalyst with high stereospecificity without mechanical grinding. In the proposed method, as in the prototype, titanium trichloride in contact with the media. Unlike the prototype, the media pretreated A1 - organic compound, and as a titanium trichloride use the resulting titanium trichloride, processed higher - olefin taken more than 50% of the titanium trichloride. Thus obtained catalyst can improve isotacticity powder polypropylene without the use of stereospecificity additives.

The invention relates to a method for producing a highly active polymerization catalyst with high stereospecificity. The use of supported catalysts containing compounds of transition metals on the surface of the media, can significantly increase the activity of the catalytic system for the polymerization of olefins. For the wide use of such rolled isatori based compounds Ti+4and V+4have low stereospecificity, which reaches a high level only when the introduction of various additives, esters, amines, organosilicon compounds [1 3] to Increase the output of regular fractions in the polymer can, securing connections Ti+4, V+4on the surface of the carriers with the crystal structure of the layered type, like purple modification TiCl3(CoCl, CrCl, MgCl) [4]

However, stereospecificity such catalysts remains lower than that of a, and - TiCl3.

The closest solution was effective and used operations is a technique in which the catalytic component prepared by the joint grinding of kaolin and titanium trichloride in the presence of Elektrodinamika connection as stereoregularity additives [5] the Grinding is carried out in a ball mill for 40 hours, the Obtained polypropylene powder has isotacticity 93,3

The disadvantage of the proposed method is the duration of the process of formation of the catalytic complex and the need for the introduction of the catalytic complex of special additives that provide stereospecificity of the obtained polymer. In addition, the result of grinding retene is to obtain a highly active catalyst for stereospecific polymerization.

The proposed method industrial microspherical titanium trichloride is mixed in heptane at room temperature with a higher olefin (1-hexene, octene-1, mission-1 or mixtures thereof) in an amount of more than 50% of trichloride titanium for carrying out the process.

Thus obtained titanium component is put under stirring in an inert solvent at a pre-activated media, which is used as the Al2O3, Cr2O3, MgO, kaolin, tuff, or other inorganic materials with a developed surface. Pre-activation of the media lies in its annealing to remove adsorbed moisture, as well as in the processing alyuminiiorganicheskikh connection (diethylaluminium, triethylaluminium). Formed on the surface of the carrier alumoxane compounds activate the media fixates on its surface resulting titanium trichloride treated with higher a - olefin. Use for pre-processing a higher olefins due to the possibility of obtaining fine catalyst, the particle size of which is commensurate with the size of the pores of the carrier and capable of deeper vzaimode is S="ptx2">

Numerous experiments have shown that the processing of higher a - olefins in the amount of 50% of the titanium component leads to a significant reduction of the particle size of microspherical catalyst (up to 1.5-2 μm). A further increase of this ratio does not affect the particle size, but dramatically increases the viscosity of the reaction medium and requires greater expenditure of a higher olefins.

Use for applying specially processed resulting titanium trichloride in comparison with the titanium trichloride used in the prototype, increase the number of active centers, which affects the activity of the catalyst.

Example 1. 10 g of silica gel in the form of particles 150-215 μm, dried in vacuum at 400oC handle (C2H5)2AlCl (JAH) when the ratio silicagel: ZACH 2,5, store in a sealed ampoule.

In a glass reactor equipped with a mixer, devices for loading of filler, solvent, catalyst, nitrogen is placed 250 ml of heptane, 10 g (65 mol) resulting titanium trichloride, 9 g (75 mol) ZACH. When mixing in the reactor make 6 g of a mixture of octene-1 and mission-1 and are processed before the termination of the heat dissipation (time media (by weight 1:1), stirred at room temperature for 1 h the Solvent is removed by vacuum.

Thus obtained catalyst contains 0.4% of titanium and provides specific output when the suspension polymerization of propylene 25 kg PP/g Ti (solvent heptane, the polymerization temperature of 65oC, pressure of propylene 96 MPa, the hydrogen concentration in the gas phase reactor 5% curing time: 2 hours

Isotacticity powder is 96%

Example 2. 10 g of talc powder is dried in vacuum at 200oC, is treated in a stream of nitrogen diethylaluminium with a ratio of talc: ZACH 2 and stored in a sealed ampoule.

Next, the process is conducted in the conditions of example 1 with the use of pre-treated talc.

Obtained by this method, the catalyst contains 1.5% titanium and provides for the suspension polymerization of propylene specific exit 13 kg PP/g Ti with isotacticity 96%

As seen from the above examples, the proposed method, the time of preparation of the catalytic component is reduced in 2 times in comparison with the prototype, increases the activity of the catalyst, stereospecificity powdery polypropylene increases to 96% vs. 93 with a coating of titanium trichloride in porous media, containing hydroxyl groups, characterized in that the carrier pretreated alyuminiiorganicheskikh compound of the formula

AlRnX3-n,

where R is alkyl;

X is hydrogen or halogen;

n 2, 3,

and as titanium trichloride use the resulting titanium trichloride, processed higher-olefin (1-hexene, octene-1, mission-1 or mixtures thereof), taken in an amount of more than 50% of the titanium trichloride.

 

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FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to butene-1 (co)polymers and a method of their synthesis. Except for, invention relates to articles made of butene-1 (co)polymers. Homopolymers of butene-1 are characterized by the following properties: (i) value of molecular-mass partition expressed as the ratio Mw/Mn based on measurement with using analysis carried out by gel-permeation chromatography method is less 6, and (ii) strength value of melt is above 2.8 g. These homopolymers are used for making tubes. Method for synthesis of butene-1 homopolymers is carried out in the presence of a stereospecific catalyst comprising (A) a solid component containing Ti compound and internal electron-donor compounds chosen from phthalates and applied on a carrier MgCl2; (B) alkylaluminum compound, and (C) tert.-hexyltrimethoxysilane as an external electron-donor compound. Butene-1 homopolymers possess a set of mechanical properties providing the presence both barostability after prolonged period time and their easy processing for making tubes.

EFFECT: valuable properties of (co)polymers, improved method of synthesis.

12 cl, 1 tbl, 3 ex

FIELD: polymer production.

SUBSTANCE: invention relates to high-stereospecific 1-butene (co)polymer and a high-activity process for producing the same. Process comprises polymerization of reactive monomer 1-butene in presence of catalyst including solid component containing titanium compound and in presence of inert gas, the latter being introduced into reactor together with hydrogen in order inert gas to be present in reactor during polymerization. This step is performed at elevated pressure in polymerization reactor owing to use inert gas at higher pressure than equilibrium pressure of gas-liquid reactant system at reaction temperature from 10 to 110°C. High-stereospecific polybutylene obtained in this process is characterized by that it is 1-butene homopolymer or copolymer including up to 40 wt % α-C2-C20-olefins other than 1-butene and shows following properties: titanium does nor present in catalyst residues at the ppm level, stereospecificity expressed through content of isotactic pentads (mmmm%) and measured using 13C-NMR technique equals 96 or higher, and molecular mass distribution (Mw/Mn) is 3-6.

EFFECT: enabled effective process for production of high-stereospecific polybutylene essentially free of catalytic residues.

3 cl, 4 dwg, 11 ex

FIELD: transport.

SUBSTANCE: method and system for unloading excess suspension from polymerisation reactor. Proposed method comprises unloading suspension from reactor onto transfer line terminating at hardening chamber, forcing suspension via heat-isolated pipeline arranged horizontally, inclined upward, or vertically, or otherwise, and along pipeline nozzle fitted through hardening chamber wall, toward transfer line outlet. It includes also feeding hardening fluid into hardening chamber adjoining pipeline nozzle. Besides, it comprises isolating pipeline nozzle from hardening chamber wall and hardening fluid. Transfer system differs in that it incorporates annular thermal barrier around pipeline nozzle that may comprises isolation and/or thermally-stable support ring, and pipeline no including catchers.

EFFECT: ruled out chocking.

19 cl, 10 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to chemistry of polymers consisting of high-molecular additives used in pipeline transport of oil and petroleum products. In said method polymerisation of higher alpha-olefins is carried out in medium of fluorinated organic compounds on titanium-magnesium catalyst with addition of electron-donor modifier, with subsequent replacement of medium of fluorinated organic compounds on dispersion medium containing anti-agglomerator, and which is higher aliphatic alcohols, glycols and mono-and di-subsituted ethers and mixture thereof. Synthesis is carried out at a given ratio of components of system. Anti-turbulent additive contains, wt%: poly-alpha-olefin (mixture of poly-alpha-olefins) 10-40; dispersion medium 48-89.9; anti-agglomerator 0.1-12.

EFFECT: disclosed is a method of producing suspension-type anti-turbulence additive in a single step based on ultrahigh molecular poly-alpha-olefins.

3 cl, 1 tbl

FIELD: organic chemistry, chemistry of polymers.

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EFFECT: improved preparing method, valuable properties of compounds.

3 cl, 2 tbl, 8 dwg, 9 ex

FIELD: polymerization processes and catalysts.

SUBSTANCE: inventors claim organometallic catalytic system for production of elastomer stereoblock polypropylene via polymerization of propylene, which system contains octahedral hexafluorine-substituted bis-acetylacetonate complex of formula (CF3COCHCOCF3)2MCl2, where M represents Ti or Zr, and, as organoaluminum compound, AlR3, where R represents ethyl, propyl, isopropyl, butyl, isobutyl, or tert-butyl, and; additionally, organomagnesium compound MgR2 or MgRX, where R is alkyl radical with 1-4 carbon atoms and X = Cl, Br, or I, M/Mg/Al molar ratio being 1.0:2.0:(100-500). Claimed is also a method for production of elastomer stereoblock polypropylene via polymerization of propylene in presence of homogenous catalyst system at transition metal complex concentration 10-3-10-5 mole/L.

EFFECT: increased catalytic activity.

2 cl, 1 tbl, 22 ex

FIELD: chemical technology, catalysts.

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EFFECT: improved preparing method, valuable properties of catalyst.

24 cl, 3 tbl, 17 ex

FIELD: chemistry of polymers.

SUBSTANCE: invention relates to mixtures of propylene polymers with improved properties comprising propylene polymers and seed charge-forming agents of crystallization wherein propylene polymers are represented by propylene homopolymers with melt indices from 0.05 to 15 g/10 min at 230°C/2.16 kg or propylene block-copolymers comprising from 90.0 to 99.9 wt.-% of propylene links and from 0.1 to 10 wt.-% of α-olefin links with 2 or 4-18 carbon atoms, melt indices from 0.05 to 20 g/10 min at 230°C/2.16 kg or their mixtures wherein propylene homopolymers or propylene block-copolymers are represented by propylene polymers with seed charge-forming agents of crystallization in β-form. Propylene homopolymers with seed charge-forming agents of crystallization in β-form have value IRτ ≥0.98, elasticity modulus at stretching ≥1500 MPa at +23°C and impact viscosity by Sharpy ≥3 kJ/m2 at -20°C with incision and propylene block-copolymers with seed charge-forming agents of crystallization in β-form have value IRτ of propylene homopolymer block ≥0.98, elasticity modulus at stretching ≥1100 MPa at +23°C and impact viscosity by Sharpy ≥6 kJ/m2 at -20°C with incision. Also, invention discloses a method for preparing mixtures of propylene polymers with seed charge-forming agents of crystallization in β-form that involves propylene homopolymers or propylene copolymers in melt with 0.0001-2.0 wt.-% of seed charge-forming agents of crystallization in β-form at temperatures in the range from 175 to 250°C. Such mixtures of propylene polymers are characterized by the presence of high rigidity and good resistance against impact charges and can be used in making the molded articles for pipeline nets, such pipes, fittings, man holes and so on.

EFFECT: improved and valuable properties of polymers.

5 cl, 5 ex

FIELD: polymer chemistry.

SUBSTANCE: invention relates to mono- or multilayered pipes and parts thereof made of propylene-based polymers for pipelines comprising propylene homopolymer having flow melt index from 0.05-8 g/10 min at 230°C/2.16 kg or propylene block-copolymer containing 90.0-99.9 mass % of propylene units and 0.1-10.0 mass % of C2- or C4-C18 α-olefin units having flow melt index from 0.05-8 g/10 min at 230°C/2.16 kg or mixtures thereof, wherein propylene polymers or propylene block-copolymers represent propylene polymers with crystal-nucleating agents in β-form hawing IRτ >=0.97. Pipelines made of propylene homopolymers with crystal-nucleating agents in β-form have fast crack spreading with critical temperature from -25 to 0°C and critical pressure of >=3 bar below critical temperature; and pipelines made of propylene block-copolymers with crystal-nucleating agents in β-form have fast crack spreading with critical temperature from -5 to +40°C and critical pressure of >=3 bar below critical temperature. Also disclosed is method for pipe production from propylene homopolymers or propylene block-copolymers by extrusion or injection molding. Pipelined of present invention are useful in conveyance of fluid media and fluid media under pressure.

EFFECT: pipes of improved cracking resistance.

4 ex, 3 cl

FIELD: rigid pipes.

SUBSTANCE: multi-layered pipe comprises at least one layer made of propylene homopolymer having melting index ranging from 0.05 to 10 g/10 min at 230°C/2.16 kg or propylene block copolymers containing 90.0-99.9 % (in mass) of links of propylene and from 0.1 to 10.0 % (in mass) of links of α-olefins having 2 or 4-18 atoms of carbon with melting indices ranging from 0.05 to 15 g/10 min at 230°C/2.16 kg.

EFFECT: expanded functional capabilities.

12 cl

FIELD: chemical industry; the methods and installations for production of the oxidized atactic polypropylene.

SUBSTANCE: the invention is pertaining to production of the oxidized atactic polypropylene with the molecular mass of 5500-38000 and the polar functional groups, which may be used as the component of the various composite materials, the multipurpose additives for lubricants, anticorrosion coatings. For production the above-indicated oxidized atactic polypropylene they use the industrial atactic polypropylene with the molecular mass of 20000-40000 and the oxidization conduct at least in two stages with the adjustable temperature drop from 250 to 150°С within 1-6 hours at the air consumption of 0.6-1.9 l/(minute·kg). The installation for the method realization contains at least two in series connected reactors supplied with the electric heater at the ratio of the height of the reactor to its diameter laying within the limits of 2.0-5.0, the device for the air supply is made in the form of the vertical pipe with the air supply through its upper part and in the lower part it is supplied with the nozzle with the slits arranged along the perimeter of the lower edge. At that the diameter of the nozzle with respect to the diameter of the reactor is chosen within the limits of 0.25-0.5.

EFFECT: the invention ensures production of the oxidized atactic polypropylene with the molecular mass of 5500-38000 and the polar functional groups, which may be used as the component of the various composite materials, the multipurpose additives for lubricants and the anticorrosion coatings.

5 cl, 1 dwg, 4 ex

FIELD: polymerization processes.

SUBSTANCE: invention relates to a process of gas-phase polymerization of olefins conducted in a separate horizontally arranged reactor and describes gas-phase (co)polymerization of propylene in reactor with piston-driven two-phase stream wherein at least one monomer stays in contact with catalytic system including: magnesium halide-supported titanium component; organoaluminum component wherein components of catalytic system are added through inlet ports located axially along the reactor; and two external electronodonor components, in particular organosilicon compounds. Subject-matter of invention consists in that addition of the first external electronodonor component to reactor is accomplished through axially arranged inlet port located near the inlet port for component comprising supported Ti-containing component and addition to reactor of at least one second external electronodonor component showing higher stereo-controlling ability than first component is accomplished through axially arranged inlet port located downstream of the inlet port for the first external electronodonor component. A gas-phase process of propylene (co)polymerization in cylindrical horizontal reactor with piston-driven two-phase stream essentially in fluidized bed is described, wherein at least one monomer stays in contact with catalytic system including: titanium component supported by magnesium halide; organoaluminum component, and at least one external silicon-containing silicon-containing electronodonor component, in which process catalytic system components are added through inlet ports arranged axially along reactor, addition of the first external electronodonor component to reactor is accomplished through inlet port located axially near the inlet for supported transition metal-containing component and addition of at least second external silicon-containing electronodonor component, showing higher stereo-controlling ability than first component is accomplished through a port located at a distance constituting at least 25% the length of reactor and downstream of the inlet port for the first external electronodonor component.

EFFECT: enabled preparation of high-stereoregular propylene homopolymers and propylene-based copolymers.

10 cl, 2 tbl, 3 ex

FIELD: polymer production.

SUBSTANCE: invention describes process of producing propylene-based polymer via polymerization of monomer in hydrocarbon solvent at 20-80°C and excessive pressure 1 to 30 atm in presence of catalyst and hydrogen as polymer molecular mass regulator, said catalyst being a product obtained by preliminary treatment of titanium trichloride and diethylaluminum chloride with propylene carried out at weight ratio Et2AlCl/TiCl3 = 1 to 10 determined by density of layer of initial TiCl3 particles within the following limits: 1-2 at density below 0.46 g/cc, 3-5 at density 0.46-0.50 g/cc, 6-10 density above 0.50 g/cc. When polypropylene is obtained, preliminary treatment of titanium trichloride and diethylaluminum chloride with propylene is carried out to achieve conversion 2.0-3.0 g polymer per 1 g TiCl3 and, when propylene/ethylene copolymer is obtained, treatment is carried out to achieve conversion 3.0-4.0 g polymer per 1 g TiCl3. After termination of pretreatment of titanium trichloride and diethylaluminum chloride with propylene and before measuring out pretreatment product into principal polymerization reactor, weight ratio Et2AlCl/TiCl3 is adjusted to fall into range 6-10 through additionally dosing calculated quantity of diethylaluminum chloride.

EFFECT: prevented breaking of catalyst particles, preserved high activity and stereospecifity thereof, and increased productivity of process.

2 cl, 2 tbl, 18 ex

FIELD: chemistry.

SUBSTANCE: invention refers to crystalline propylene polymers with high stereoregularity, specifically high content of isotactic pentalogies, improved processability in molten state and to production method. Propylene polymer is produced with the following properties: isotactic pentalogies content, measured by nuclear magnetic resonance (NMR), is higher than 98%, chain-length distribution expressed by ratio is from 6 to 11, and value of ratio is equal or lower than 5.5. Specified polymer is produced with special combination of solid components of Zigler-Natt catalyst and highstereoregular electron-donor compounds. Film or plate is made of propylene polymers having said properties. Sandwiched laminated product comprises specified film or plate. Films and plate are characterized by good homogeneous thickness, as well as high ultimate elongation and high ultimate tensile strength.

EFFECT: propylene polymers are more easily recycled.

9 cl, 4 tbl, 8 ex

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